Hydrogen storage material analyzer and analysis and activation methods

ABSTRACT

A hydrogen storage material analyzer along with its analysis and activation methods, the hydrogen storage material analyzer including a H 2  absorption-desorption cycling tester, a temperature-programmed desorption spectrometer, a specimen holder and a temperature-controlled furnace. With this hydrogen storage material analyzer, a complete set of instruments can be used to implement simultaneously cyclic hydrogenation-dehydrogenation test and thermodynamic desorption analyses, thus improving the working efficiency and analysis accuracy.

CROSS-REFERENCE TO RELATED U.S. APPLICATIONS

Not applicable.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

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NAMES OF PARTIES TO A JOINT RESEARCH AGREEMENT

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REFERENCE TO AN APPENDIX SUBMITTED ON COMPACT DISC

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BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to a hydrogen storage material analyzer, and more particularly to an innovative one which involves hydrogenation degradation analysis and activation methods.

2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 37 CFR 1.98.

Hydrogen technology is extensively applied in the fields of the syntheses of methanol and ammonia, hydrogen engine, hydrogen fuel cell and fossil industries. Hydrogen fuel cells are characterized by higher operating efficiency and zero pollution.

Due to the advantages of hydrogen technologies, the hydrogen storage materials have gained great attention. For instance, the Ti₂₅V₃₅Cr₄₀ hydrogen storage alloy with the reversible hydrogen storage capacity of 1.8 wt. % at room temperature is larger than conventional LaNi₅ hydrogen storage alloy (1.2 wt. %). After adding 0.1% carbon, the hydrogen desorption pressure of Ti₂₅V₃₅Cr₄₀ is increased, thus enhancing the effective hydrogen desorption capacity at room temperature about 8-20%. As such, this kind of hydrogen storage alloy has a unique potential of commercialization and academic study.

The hydrogenation reaction of hydrogen storage material is accompanied by reactive heat. Since the hydrogenation is reversible, a lot of hydrogen gas can be stored, with an exothermic reaction during absorption and endothermic reaction during desorption. Hence, the utilization quality of hydrogen storage material is crucial to its absorption and desorption properties. However, irrespective of the performance of hydrogen storage material, ageing and degradation problems will be encountered over time. Said ageing and degradation phenomenon may be caused by intrinsic microstructure change of hydrogen storage material, or loss of absorption/desorption capability due to the surface covered by the extrinsic impurities in the hydrogen source. In the practice, these problems have to be characterized by specifically designed analyzers, therefore, the hydrogen storage material analyzer plays a decisive role in the development of high performance hydrogen storage material.

The existing hydrogen storage material analyzers are currently categorized into two types: H₂ absorption-desorption cycling testers, and temperature programmed desorption (TPD) spectrometers. The former one is intended for ageing test through cyclic hydrogen absorption-desorption, while the latter one is devoted to the dehydrogenation thermodynamics of hydrogen storage materials.

The above two hydrogen storage material analyzers along with their technologies are represented by different functions and significance. However, as these two instruments are operated separately, it is difficult to guarantee consistent analyses of hydrogen storage material, and in other words, the samples must be placed on the cyclic hydrogen absorption-desorption tester in the first phase, and then removed and shifted to TPD for analysis and test in the second phase. In such a case, this will lead to not only inefficient analysis, but also error arising from sample removal, thus affecting the final accuracy and quality of analysis and testing.

Thus, to overcome the aforementioned problems of the prior art, it would be an advancement if the current art can provide an improved design that can significantly increase the accuracy and efficacy of analysis and testing.

Therefore, the inventor has provided the present invention of practicability after deliberate experimentation and evaluation based on years of experience in the production, development and design of related products.

BRIEF SUMMARY OF THE INVENTION

Based on the unique configuration of the present invention wherein “the hydrogen storage material analyzer along with its analysis and activation methods” mainly comprises: a H₂ absorption-desorption cycling tester, a temperature-programmed desorption spectrometer, a specimen holder and a temperature-controlled furnace, a complete set of instruments can be used to implement simultaneously cycling desorption test, desorption analysis and activation requirements, thus eliminating the problem of removing the samples to another instrument for the intended purposes. Hence, the present invention presents better working efficiency, higher analysis accuracy and quality.

Although the invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a schematic view of the hydrogen storage material analyzer of the present invention indicating hydrogen supply of the hydrogen cylinder.

FIG. 2 is a schematic view of the present invention wherein the specimen valve is opened to guide hydrogen into the specimen holder.

FIG. 3 is a sectional view of the specimen holder of the present invention indicating the hydrogen absorption state of the hydrogen storage material.

FIG. 4 is a schematic view of the hydrogen storage material with hydrogen desorption state of the present invention.

FIG. 5 is a schematic view of the present invention wherein the mass spectrometer is used for desorption analysis of the hydrogen storage material.

FIG. 6 is a cycling degradation curve of Ti₂₅V₃₅Cr₄₀ hydrogen storage material in a hydrogen test (purity 99.9999%).

FIG. 7 is a comparison view of TPD spectra of Ti₂₅V₃₅Cr₄₀ hydrogen storage material before/after 500 cycles.

FIG. 8 is a PCI curve of Ti₂₅V₃₅Cr₄₀ hydrogen storage material before/after 500 cycles.

FIG. 9( a) shows a XRD diffraction pattern of Ti₂₅V₃₅Cr₄₀ hydrogen storage material before/after 500 cycles.

FIG. 9( b) show peaks for Ti-rich precipitate tested in a slow diffraction mode (lo/min).

FIG. 10 shows hydrogenation degradation curves of the hydrogen storage material of the present invention (purity 99.99%).

FIG. 11( a) shows variation of hydrogen absorption pressures of the hydrogen storage material during the cycles.

FIG. 11( b) shows hydrogen desorption pressure of the hydrogen storage material during the cycles.

FIG. 12 shows a TPD spectra between activated and poisoned alloys after 150 cycles.

FIG. 13( a) shows TPD-MS spectra of poisoned alloys for N₂/CO.

FIG. 13( b) shows TPD-MS spectra of poisoned alloys for H₂.

FIG. 13( c) shows TPD-MS spectra of poisoned alloys for H₂O.

FIG. 13( d) shows TPD-MS spectra of poisoned alloys for H₂S.

FIG. 14 is a schematic view of extrinsic hydrogenation degradation of hydrogen storage material in the present invention.

FIG. 15 shows a comparison of PCI curves of hydrogen storage material in the condition of activated and re-activated in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

FIGS. 1-2 depict preferred embodiments of a hydrogen storage material analyzer of the present invention along with analysis and activation method, which, however, are provided for only explanatory objective for patent claims.

Said hydrogen storage material analyzer A comprising: a H₂ absorption-desorption cycling tester 10, a temperature-programmed desorption spectrometer 20, a specimen holder 30 and a temperature-controlled furnace 40. The specimen holder 30 is used to load the hydrogen storage material 50 (marked in FIGS. 3, 4).

The H₂ absorption-desorption cycling tester 10 includes a hydrogen cylinder 11, a hydrogen reservoir 12 and a hydrogen pipeline 13. The first end 131 of the hydrogen pipeline 13 is linked to the hydrogen cylinder 11, and the second end 132 of the hydrogen pipeline 13 is connected to the specimen holder 30. The first end 131 of the hydrogen pipeline 13 is fitted with an inlet valve 14 to control the on/off state of hydrogen supply from the hydrogen cylinder 11. The hydrogen reservoir 12 is linked to the hydrogen pipeline 13 via a bypass flow channel 15. The second end 132 of the hydrogen pipeline 13 is fitted with a specimen valve 17 to control the connection state between the hydrogen pipeline 13 and specimen holder 30. Moreover, a first pressure gauge 18 is arranged onto the hydrogen pipeline 13 between the specimen valve 17 and inlet valve 14.

The temperature-programmed desorption spectrometer 20 includes a hydrogen desorption channel 21, a vacuum pump 22 and a mass spectrometer 23. The hydrogen desorption channel 21 is provided with a first end 211 to link the second end 132 of the hydrogen pipeline 13 of the H₂ absorption-desorption cycling tester 10. The mass spectrometer 23 is linked to the second end 212 of the hydrogen desorption channel 21. The mass spectrometer 23 is set in front of the vacuum pump 22. A second pressure gauge 24 is arranged between the vacuum pump 22 and the first end 211 of the hydrogen desorption channel 21.

An integrated joint 60 is used to couple the second end 132 of the hydrogen pipeline 13 of the H₂ absorption-desorption cycling tester 10 with the first end 211 of the hydrogen desorption channel 21 of the temperature-programmed desorption spectrometer 20. Moreover, the integrated joint 60 is provided with a joint valve 61 to control the connection state of the hydrogen pipeline 13 and hydrogen desorption channel 21.

Furthermore, the temperature-controlled furnace 40 is used for temperature control of the specimen holder 30, while the specimen holder 30 is provided with a specimen space 31 (see FIG. 3) to load the hydrogen storage material 50.

Based on the above-specified structural configuration, the analysis and activation methods for the hydrogen storage material analyzer A are described below:

First, automatic cycling absorption and desorption methods of the present invention are briefed below:

The structural configuration of the hydrogen storage material analyzer A of the present invention is shown in FIG. 1, wherein the system framework is composed of electronic control unit, hydrogen pipeline and temperature-controlled furnace. Said electronic control unit comprises a personal computer, signal input/output interface card, relay control interface card and electromagnetic valve assembly. As for the hydrogen storage material analyzer A of the present invention, the cyclic absorption and desorption steps are described as follows:

a. The electromagnetic valve assembly is controlled by a program, and the electromagnetic valve is used to activate the working gas flow (5 kg/cm²) to the designated actuator chamber of pneumatic valve, enabling automatic hydrogen charging and discharge for hydrogen storage material.

b. Take hydrogen-charging process as a example: the reaction temperature of the hydrogen storage material is controlled at a constant temperature (e.g.: 30 degrees C.). When the inlet valve 14 is opened by a computer, hydrogen H₂ starts to enter into the hydrogen reservoir 12 (see FIG. 1), and the pressure reading is sent back to the computer. When the H₂ pressure conforms to the setting value, the inlet valve 14 is shut down immediately (see FIG. 2, represented by blacking), then the specimen valve 17 is opened, allowing hydrogen H₂ to enter into the specimen holder 30, so that hydrogen storage material 50 (e.g.: hydrogen storage alloy) in the specimen holder 30 starts to absorb hydrogen (see FIG. 3).

c. When the pressure reading drops over time, the hydrogen storage material 50 starts to absorb hydrogen, during which the kinetics curve is recorded by the computer, and the hydrogen absorption of hydrogen storage material 50 (wt. %) is calculated by the pressure difference. After the absorption reaction is equilibrated, the joint valve 61 of the integrated joint 60 is opened to discharge hydrogen stored in the hydrogen storage alloy (see FIG. 4), thus finishing a cycle of absorption and desorption of hydrogen storage material 50.

Additionally, the cyclic hydrogenation-dehydrogenation performance of hydrogen storage material 50 can be measured and monitored by a program-controlled process.

The analysis and activation methods of the hydrogen storage material of the present invention are described below:

1. Intrinsic hydrogenation degradation:

Through programmed operation of on/off for the valves in the H₂ absorption-desorption cycling tester 10 and temperature-programmed desorption spectrometer 20, hydrogenation degradation of Ti₂₅V₃₅Cr₄₀ hydrogen storage material are observed after 500 cycles of absorption and desorption using 6N hydrogen as shown in FIG. 6, the degradation is about 16.5%. The hydrogenation degradation mechanism of common alloy is divided into intrinsic and extrinsic degradation. To further analyze 16.5% hydrogenation degradation of Ti₂₅V₃₅Cr₄₀ hydrogen storage material, extrinsic degradation must be firstly considered; after 500 cycles of test, long-lasting dehydrogenation at room temperature is conducted, allowing the hydrogen storage material to be as β hydride within the specimen holder 30. The TPD spectrum in this state is shown in FIG. 7, wherein the TPD curve of β hydride before/after cycling differs little, thus demonstrating that the extrinsic factors to degrade hydrogen storage material are eliminated.

Hydrogenation degradation of Ti₂₅V₃₅Cr₄₀ hydrogen storage material after 500 cycles of test is caused by intrinsic factors as indicated by the variation of PCI (Pressure-Composition-Isotherm) curve in FIG. 8. Maximum hydrogen absorption of hydrogen storage material drops from 3.52 wt. % to 3.23 wt. %, with a degradation about 8.2%, and the hydrogen pressure within the specimen holder 30 rises. Besides, it is found from XRD diffraction experiment that (see FIG. 9), for the hydrogen storage material after 500 cycles of test, the diffraction angle shifts towards a higher angle, showing the reduction of lattice constant, and accounting for the rising flat pressure of absorption. Meanwhile, minor diffraction peak (see FIG. 9) occurs nearby 2θ=38.5° and 40°, and is assigned as Ti-rich precipitate. As the radius of titanium, vanadium and chrome is 0.145, 0.132 and 0.125 nm, respectively, the formation of this precipitate will lead to reduction of both titanium concentration within Ti₂₅V₃₅Cr₄₀ matrix and Ti₂₅V₃₅Cr₄₀ lattice constant.

2. Extrinsic hydrogenation degradation:

Extrinsic hydrogenation degradation is tested by taking 5N hydrogen as gas source or by adding toxic microelement CO, H₂S, CO₂, H₂O, etc, and then the degradation of Ti₂₅V₃₅Cr₄₀ alloy reacting with hydrogen source of lower purity is observed. The resulting findings are shown in FIG. 10, wherein after 33 cycles of tests, serious hydrogenation degradation of Ti₂₅V₃₅Cr₄₀ hydrogen storage material occurs (down from 1.6 wt. % to 0 wt. %).

To understand the reason of degradation, the cycling hydrogenation properties including the hydrogen absorption/desorption pressure as function of cycle are monitored shown in FIG. 11. It is found that, the hydrogen absorption stops gradually over time, showing that serious degradation of hydrogen storage material occurs or hydrogen desorption is disabled due to obstruction. On the other hand, as shown in FIG. 12, it is observed from degraded alloy's TPD spectrum (TPD spectrum is generated by the second pressure gauge 24 of temperature-programmed desorption spectrometer 20) that, there is not any dehydrogenation signal from room temperature to 160° C., but there are two dehydrogenation peaks at about 210° C. and 300° C., representing dehydrogenation of titanium alloy's δ→β and β→α hydride. As the former one's, appropriate dehydrogenation temperature is room temperature and it can be seen that poisoning of hydrogen storage alloy may occur in such case. Thus, loss of hydrogen absorption/desorption capability is attributed to the surface of hydrogen storage material covered by impurities in the hydrogen source. Moreover, it is proved that dehydrogenation temperature ofpoisoned Ti₂₅V₃₅Cr₄₀ is 160° C. Hence, re-activation temperature ofpoisoned hydrogen storage material should be set above this temperature.

Toxic substance is originated from impurities from hydrogen source, impeding the formation of hydride by reacting hydrogen with alloy. Referring also to FIG. 13, it is found from TPD-MS spectra (this signal is generated by mass spectrometer of temperature-programmed desorption spectrometer), with the temperature rise of hydrogen storage material, some substances, such as: H₂, H₂ O, CO, O₂ and H₂ S, are desorbed from the surface. It is clear that hydrogenation poisoning of hydrogen storage material is caused from the alloy surface covered by toxic substance (see FIG. 14), thus reducing greatly the hydrogenation capability of hydrogen storage material. Meanwhile, dissociation temperature of TPD-MS spectra is defined as the dehydrogenation temperature of poisoned hydrogen storage material, and re-activation temperature of poisoned hydrogen storage material will be above this temperature. After temperature programmed dehydrogenation, a PCI curve (see FIG. 15) of the degraded hydrogen storage material is observed, showing that the flat pressure and maximum absorption, etc, are the same with original alloy. Thus, it is judged that hydrogenation degradation of the hydrogen storage material is not derived from the change of microstructure.

3. Re-activation of hydrogen storage material: (see FIG. 5)

After extrinsic hydrogenation degradation of the hydrogen storage material is confirmed, it is required to shut down the inlet valve 14 for the first end 131 of the hydrogen pipeline 13, and open the joint valve 61 for the first end 211 of the hydrogen desorption channel 21, then start the temperature-controlled furnace 40 to heat up the specimen holder 30. Moreover, the heating temperature is controlled over a dehydrogenation temperature, e.g.: 160° C., so as to dispel toxic substances covered on the surface of the hydrogen storage material. Next, the vacuum pump 22 of the temperature-programmed desorption spectrometer 20 is started to discharge the toxic substances for reactivation of the hydrogen storage material. 

1. A hydrogen storage material analyzer; comprising: a hydrogen absorption-desorption cycling tester, a temperature-programmed desorption spectrometer, a specimen holder and a temperature-controlled furnace; of which: the hydrogen absorption-desorption cycling tester includes a hydrogen cylinder, a hydrogen reservoir and a hydrogen pipeline; the first end of the hydrogen pipeline is linked to the hydrogen cylinder, and the second end of the hydrogen pipeline connected to the specimen holder; the first end of the hydrogen pipeline is fitted with a inlet valve to control the on/off state of hydrogen supply from the hydrogen cylinder; the hydrogen reservoir is linked to the hydrogen pipeline via a bypass flow channel; the second end of the hydrogen pipeline is fitted with a specimen valve to control the connection state between the hydrogen pipeline and specimen holder; moreover, a first pressure gauge is arranged onto the hydrogen pipeline between the inlet valve and specimen valve; the temperature-programmed desorption spectrometer includes a hydrogen desorption channel and a vacuum pump; the hydrogen desorption channel is provided for the hydrogen pipeline of the hydrogen absorption-desorption cycling tester; a second pressure gauge is arranged between the vacuum pump and the first end of the hydrogen desorption channel; an integrated joint is used to couple the second end of the hydrogen pipeline of the hydrogen absorption-desorption cycling tester with the first end of the hydrogen desorption channel of temperature-programmed desorption spectrometer; moreover, the integrated joint is provided with a joint valve to control the connection state of the hydrogen pipeline and hydrogen desorption channel; Furthermore, the temperature-controlled furnace is used to heat specimen holder, while the specimen holder is provided to load hydrogen storage materials; when the inlet valve is opened, hydrogen starts to enter into the hydrogen reservoir; if the hydrogen pressure reaches to the setting value, the inlet valve is shut down, then the specimen valve is opened to guide hydrogen into the specimen holder, enabling hydrogen absorption of the hydrogen storage material; after hydrogen absorption reaction is in equilibrium, the integrated joint valve is opened to discharge hydrogen stored in the hydrogen storage materials, thus finishing a cycle of absorption and desorption of hydrogen.
 2. The device defined in claim 1, wherein said a temperature-programmed desorption spectrometer comprises of a mass spectrometer, which is linked to the second end of the hydrogen desorption channel, and set in front of the vacuum pump.
 3. The analysis method defined in claim 1, wherein the performance analysis of the hydrogen storage material analyzer is used to examine the intrinsic hydrogenation degradation, including: a. When the hydrogen storage material is conducted with the set cycles of hydrogen absorption/desorption, the cycled hydrogen storage material is dehydrided at room temperature for a long time; b. the cycled hydrogen storage material is kept within the specimen holder to avoid any contamination caused by specimen handing during analysis procedure; c. TPD spectrum obtained is used to exclude any extrinsic factor to contaminate the hydrogen storage material; d. the cycled hydrogen storage material is verified to be caused by intrinsic degradation if it is derived from the change of material properties, according to maximum hydrogenation capacity decline, degradation rate and variation of absorption hydrogen pressure during cycling.
 4. The analysis method defined in claim 1, wherein the performance analysis of the hydrogen storage material analyzer is used to examine the extrinsic hydrogenation degradation, including: a. the degradation of hydrogen storage material in the specimen holder is tested by taking lower purity hydrogen gas or by adding some toxic molecules likes CO, H₂ S, CO₂, H₂ O etc. to H₂ gas; b. when the cycling hydrogen absorption and desorption of the hydrogen storage material is conducted, the hydrogen pressure for absorption and desorption reaction stops gradually over time, so the hydrogenation degradation property is obtained showing that serious degradation of hydrogen storage material occurs or desorption is disabled due to extrinsic obstruction; c. the dehydriding temperature of cycled hydrogen storage material is obtained from TPD spectrum recorded by the second pressure gauge in the temperature-programmed desorption spectrometer; thus verifying whether the loss of hydrogen storage in the materials is caused by extrinsic poisoning covered on the surface of materials; d. a mass spectrometer is used in the temperature-programmed desorption spectrometer to measure the temperature programmed-desorption and mass (TPD-MS) curve of hydrogen storage materials, helping to examine the types and amount of impurities desorbed from the degraded hydrogen storage material, and characterize the adsorption strength of impurities with the cycled hydrogen storage materials to provide a basis for developing high-performance hydrogen storage material against extrinsic hydrogenation degradation; e. a temperature programmed dehydrogenation treatment is applied for the degrade hydrogen storage materials, helping to obtain the flat pressure and maximum absorption properties of degraded hydrogen storage material shown in a PCI curve, which are the same with original hydrogen storage material, so the hydrogenation degradation of the hydrogen storage material is not derived from the change of microstructure.
 5. The method defined in claim 4, wherein said TPD or TPD-MS spectra can be used to obtain the dehydrogenation temperature.
 6. The activation method of hydrogen storage material defined in claim 1, wherein the activation method of said hydrogen storage material analyzer is used to re-activate the degrade hydrogen storage material, including: a. confirm that the hydrogenation degradation of materials resulted from extrinsic factors; b. close the inlet valve of the hydrogen pipeline, open the joint valve of the hydrogen desorption channel, and then restart the temperature-controlled furnace to heat up the specimen holder; c. set the temperature of temperature-controlled furnace over the dehydrogenation temperature obtained from TPD or TPD-MS spectra; d. start the vacuum pump of temperature-programmed desorption spectrometer to discharge toxic substances adsorbed on the hydrogen storage material for re-activation purpose. 